Use of a solvent/antifoam substance mixture in aqueous formulations and resulting formulations

ABSTRACT

The invention relates to the application, in an aqueous formulation, of a mixture comprising at least one solvent and at least one substance having antifoam properties in aqueous medium; the solvent/substance weight ratio is between 99.95/0.05 and 90/10; said solvent is chosen from those for which, in all or part of the range of the abovementioned weight ratio, the mixture is homogeneous, and from those for which the aqueous formulation, comprising from 0.01 50 5% by weight of mixture, is homogeneous.

The subject of the present invention is the use of a mixture comprisinga solvent and a substance having antifoam properties in aqueousformulations.

In numerous fields using aqueous formulations, it is necessary tocontrol the level of foam produced, or even to avoid its appearance,this being even more critical if the formulations comprise a relativelyhigh content of surfactants. These compounds not only promote theappearance of foam but also enhances its stability.

There are various reasons for wishing to achieve such a result.

For example, the appearance of a more or less stable foam, in anexcessively large quantity can cause difficulties during the manufactureand/or the packaging of formulations, resulting in a loss ofproductivity at this (these) stage(s) of production.

Foam can also be a problem when it appears during the use of theformulations. In this case, it can be the cause of overflowing of tanks,of difficulties during the application of the formulation with inparticular poor operation of the pumps used. Foam can also causeuncontrolled and large variations in the viscosity of the formulation.Moreover, in the case of cement formulations used in the field ofbuilding materials or of the exploitation of oil or gas deposits, theappearance of foam can be the cause of a reduction in the performance ofthe formulation, the reduction in performance due to the presence of airbubbles trapped in the formulation during setting.

Apart from the difficulties mentioned above, the phenomenon of foamingcan prove to be dangerous in applications linked to the cleaning ofplatforms. Indeed, not only can the platforms be made slippery but alsothe appearance of foam in the well itself, during the cleaning operationof the latter before it goes into production, has the consequence ofreducing the density in the well (by inclusion of air) and can, forexample, cause uncontrolled eruption of petroleum if it involves agusher.

In order to solve these disadvantages linked to the appearance of foamwith certain aqueous formulations, the use of substances having antifoamproperties has been developed. However, in many cases, said antifoamsubstances are not substances soluble in aqueous medium. Thus, it ispossible to observe phenomena of incompatibility with the formulation,which can cause for example demixing or precipitation, thereby limitingthe efficacy of such substances.

The document WO 00/17266 describes an antifoam mixture comprising 70% byweight of a solvent and 30% by weight of an antifoam agent. This mixturehas beneficial effects in the context of a use in weakly basiccompositions for washing gas, in particular for removing toxic gasessuch as H₂S or CO₂. These mixtures are found to be advantageous inantifoam performance in these compositions. However, they are notadvantageous in aqueous formulations which are desired to be homogeneousand/or sufficiently stable during storage, in the presence of certaincompounds.

In some cases, such as that of aqueous formulations intended for thetreatment of plants, there has been put in place the use of additionaladditives introduced by the user during the use of the plant-protectionformulation (tank-mix). More particularly, numerous plant-protectionformulations exist in a concentrated form which the user must dilutebeforehand, in which dilution step it is possible to observe theappearance of a large quantity of foam upon application to the plant tobe treated. It is during this which is very often stable. Thus, it isduring this step that it is proposed to introduce the antifoam agent.However, this solution is not completely satisfactory in the sense thatit requires the use of several products which have to be measured outand stored.

Moreover, if these conventional additional additives, which are usuallyfluorinated silicones or metal salts of fatty acids, are added to theconcentrated aqueous formulation, the latter is not homogeneous andphase separation is observed during its storage.

It therefore still remains desirable to find additives which could beincorporated into an aqueous formulation, whether it is in concentratedor dilute form, without observing destabilization of the whole, andwhich would have antifoam and/or defoaming properties during thedilution and/or use of the aqueous formulation.

The subject of the present invention is the use, in an aqueousformulation, of a mixture comprising at least one solvent and at leastone substance having antifoam properties in aqueous medium; thesolvent/substance weight ratio being between 99.95/0.05 and 90/10; saidsolvent being chosen from those for which, in all or part of the rangeof the abovementioned weight ratio, the mixture is homogeneous, and fromthose for which the aqueous formulation, comprising from 0.01 to 5% byweight of mixture, is homogeneous.

Another subject of the invention consists of an aqueous formulationcomprising from 0.01 to 5% by weight of a mixture comprising at leastone solvent and at least one substance having antifoam properties inaqueous medium; the solvent/substance weight ratio being between99.95/0.05 and 90/10; said solvent being chosen from those for which, inall or part of the range of the abovementioned weight ratio, the mixtureis homogeneous, and from those for which the aqueous formulation,comprising from 0.01 to 5% by weight of mixture, is homogenous.

This mixture provides a solution to the problem of foaming which appearsduring the manufacture, dilution and use of the formulation. It hasindeed been observed, completely unexpectedly, that the use of this typeof mixture made it possible to destabilize the foam which appears whenthe content of antifoam agent present in the formulation is low.

It has been observed, unexpectedly, that a synergy exists, which can beobserved at two levels, between the solvent and the associated antifoamsubstance.

The first level is that of the performance achieved. Thus, in the casewhere the antifoam substance is not compatible with the aqueousformulation, it is observed, for identical concentrations (1% by weightof the formulation), that the defoaming or antifoam phenomenon isgreater for aqueous formulations comprising the abovementioned mixturethan for aqueous formulations comprising only the solvent or only theantifoam substance. It is specified that an aqueous formulationcomprising 1% of noncompatible antifoam substance in aqueous medium isof course not stable over time. Consequently, if the concentratedformulation is diluted immediately after preparation, the antifoameffect is indeed observed. However, this effect cannot be maintained inthe short term (that is after storage) unless the formulation isperfectly rehomogenized, which represents a serious constraint which itis not always possible to carry out.

The second level is that of the content of antifoam substance present inthe aqueous formulation. Thus, the results obtained with the mixtureused in the context of the invention were obtained with antifoamsubstance contents of the order of 0.01% in the formulation, or evenless.

Finally, the formulation comprising the mixture according to theinvention, whether in dilute or nondilute form, is stable during storageunlike formulations comprising contents of the order of 1% as antifoamsubstance.

However, other advantages and characteristics of the present inventionwill emerge more clearly on reading the description and the examplewhich follows.

In the text which follows, the term “mixture” will be used for thecombination of the solvent and of the antifoam substance used in thecontext of the invention.

It is furthermore specified, in the text which follows, that the termsantifoam and defoaming will be used interchangeably.

As was indicated above, the mixture used according to the inventioncomprises at least one solvent, and at least one substance havingantifoam properties in aqueous medium, the solvent/substance weightratio being between 99.95/0.05 and 90/10. This ratio ispreferably-between 99.95/0.05 and 95/5, and still more preferablybetween 99.95/05 and 98/2.

The solvent is chosen from those for which, in all or part of the rangeof abovementioned weight ratio, the mixture is homogeneous. Furthermore,the solvent is chosen from those for which the aqueous formulation,comprising from 0.01 to 5% by weight of mixture, is homogeneous.

The term homogeneous means that no decantation or macroscopic phaseseparation is observed either for the solvent/antifoam substancemixture, or for the mixture/aqueous formulation combination, at 20° C.,one hour after being brought into contact.

Among the suitable solvents, there may be mentioned:

-   -   esters of saturated or unsaturated, linear or branched mono- or        dicarboxylic acids comprising 2 to 15 carbon atoms, optionally        comprising an alkoxy group, preferably a methoxy group, or a        hydroxyl group, and of a saturated or unsaturated, linear or        branched monoalcohol or polyol comprising 1 to 13 carbon atoms;    -   the mono-, di- and/or triester phosphates for which the        radical(s), which are identical or different, are linear or        branched alkyl radicals bearing 2 to 12 carbon atoms;    -   ketones for which the radicals, which are identical or        different, are linear or branched alkyl radicals comprising 1 to        5 carbon atoms;    -   heterocyclic derivatives comprising at least one nitrogen and/or        at least one oxygen and/or at least one sulfur;    -   mono- or polyethers of polyalcohols;        alone or as a mixture.

As regards the esters of carboxylic acids, the latter are moreparticularly chosen from esters of acetic, caprylic, octanoic, decanoic,dodecanoic, lauric and lauroleic acids, alone or as mixtures.

In the case where the acid is a dicarboxylic acid, preferably the twocarboxyl functional groups are in esterified form.

Moreover, the alcohol from which the ester is formed is preferably amonoalcohol.

It will be no departure from the present invention to use the productsderived from alcoholysis (more particularly methanolysis, ethanolysis)of triglycerides of animal origin or preferably of plant origin. By wayof examples of suitable triglycerides, there may be mentioned peanutoil, cottonseed oil, linseed oil, olive oil, palm oil, grapeseed oil,soybean oil, castor oil, rapeseed oil, copra oil, coconut oil.

As regards the phosphate esters, the latter correspond more particularlyto the following formula: (RO)_(n)P(═O)(OM)_(3-n); in which R, which areidentical or not, represent a saturated or unsaturated, linear ornonlinear C₁-C₁₈, preferably C₂-C₁₂, hydrocarbon radical; n is aninteger between 1 and 3; M, which are identical or not, represent ahydrogen atom, an alkali or alkaline-earth metal, a radical of theN(R′)₄ ⁺ type for which the radicals R′, which are identical ordifferent, represent a hydrogen atom or a saturated or unsaturated,linear or nonlinear C₁-C₆ hydrocarbon radical optionally substitutedwith a hydroxyl group.

There may be mentioned in particular mono-, di- and tributyl phosphates,alone or as a mixture.

Among the suitable ketones, there may be mentioned acetone, methyl ethylketone, methyl isobutyl ketone, alone or as a mixture.

As regards the heterocyclic derivatives, comprising at least onenitrogen and/or one oxygen and/or one sulfur, suitable in particular areN-methylpyrrolidone, tetrahydrofuran, dioxane and the like;N-methylpyrrolidone being preferred.

As for the mono- or polyethers of polyalcohols, they are preferably suchthat the ether part(s) comprise one or more alkyl radicals comprisingfrom 1 to 4 carbon atoms. As for the part derived from the polyalcohol,the latter is preferably of the polyethylene glycol type. By way ofexample, there may be mentioned methyl diglycol.

Preferably, the solvent used is chosen from esters of mono- ordicarboxylic acids or the heterocyclic derivatives.

The substance having antifoam properties in aqueous medium may be chosenfrom all the compounds having this type of properties.

However, according to a first advantageous embodiment of the presentinvention, said substance is chosen from silicones.

More particularly, said silicone substances may comprise, in addition tosilicon, oxygen, carbon and hydrogen atoms, halogen atoms or nitrogenatoms.

However, advantageously, the silicone substances used are chosen fromthose comprising or consisting of units of formulaR′_(3-a)R_(a)SiO_(1/2) and R₂SiO_(2/2)in which formulae

-   -   a is an integer from 0 to 3    -   the radicals R are identical or different and represent    -   a saturated or unsaturated aliphatic hydrocarbon group        containing from 1 to 10 carbon atoms;    -   a polar organic group attached to the silicon by a Si—C or        Si—O—C bond;    -   an aromatic hydrocarbon group containing from 6 to 13 carbon        atoms;    -   the radicals R′ are identical or different and represent    -   an OH group;    -   an alkoxy or alkenyloxy group containing from 1 to 10 carbon        atoms;    -   an aryloxy group containing from 6 to 13 carbon atoms;    -   an acyloxy group containing from 1 to 13 carbon atoms;    -   a cetiminoxy group containing from 1 to 8 carbon atoms;    -   an amino or amido functional group containing from 1 to 6 carbon        atoms, attached to the silicon by an Si—N bond;        preferably at least 80% of the radicals R of said oils, gums or        resins representing a methyl group.

Among the polyorganosiloxane resins which may be used, there may bementioned those consisting of units of formula

-   -   RSiO_(3/2)(T unit) and/or SiO₂(Q unit) combined with units of        formula    -   R′_(3-a)R_(a)SiO_(1/2)(M unit) and/or R₂SiO_(2/2)(D unit) in        which formulae a, R and R′ have the definition given above.

These are generally of the MQ, MDQ, TDM, TD, MT type.

By way of examples of aliphatic or aromatic hydrocarbon radicals R,there may be mentioned:

-   -   alkyl groups such as methyl, ethyl, octyl, trifluoropropyl    -   alkoxyalkylene groups such as —CH₂—CH₂—O—CH₃; —CH₂—CH₂—O—CH₃    -   alkenyl groups such as vinyl, alkyl, hexenyl, decenyl,        decadienyl    -   alkenyloxyalkylene groups such as —(CH₂)₃—O—CH₂—CH═CH₂;        —(CH₂)₃—OCH₂—CH₂—O—CH═CH₂    -   aryl groups such as phenyl.

By way of examples of polar organic groups R, there may be mentioned:

-   -   hydroxy functional groups such as —(CH₂)₃—OH; —(CH₂)₄N        (CH₂CH₂OH)₂; —(CH₂)₃—N(CH₂CH₂OH)—CH₂—CH₂—N(CH₂CH₂OH)₂    -   amino functional groups such as —(CH₂)₃—NH₂;        —(CH₂)₃—NH—(CH₂)₂NH₂    -   amido functional groups such as        —(CH₂)₃—N—(COCH₃)—(CH₂)₂NH(COCH₃)    -   carboxyl functional groups such as —CH₂—CH₂—S—CH₂—COOH.

By way of examples of radicals R′, there may be mentioned:

-   -   alkoxy groups such as methoxy, ethoxy, octyloxy    -   alkenyloxy groups such as vinyloxy, hexenyloxy, isopropenyloxy    -   aryloxy groups such as phenyloxy    -   acyloxy groups such as acetoxy    -   cetiminoxy groups such as ON═C(CH₃)C₂H₅    -   amino functional groups such as ethylamino, phenylamino    -   amido functional groups such as methylacetamido.

By way of concrete examples of “D units”, there may be mentioned:(CH₃)₂SiO; CH₃(CH═CH₂)SiO; CH₃(C₆H₅)SiO; (C₆H₅)₂SiO; CH₃HSiO;CH₃(CH₂—CH₂—CH₂OH)SiO.

By way of concrete examples of “M units”, there may be mentioned:(CH₃)₃SiO_(1/2); (CH₃)₂(OH)SiO_(1/2;) (CH₃)₂(CH═CH₂) SiO_(1/2);(CH₃)₂HSiO_(1/2); (OCH₃)₃SiO_(1/2); [O—C(CH₃)═CH₂]₃SiO_(1/2);[ON═C(CH₃)]₃SiO_(1/2); (NH—CH₃)₃SiO₁₂; (NH—CO—CH₃)₃SiO_(1/2).

By way of concrete examples of “T units”, there may be mentionedCH₃SiO_(3/2); (CH═CH₂)SiO_(3/2); HSiO_(3/2).

When said oils, gums or resins contain reactive and/or polar radicals R(such as H, vinyl, allyl, hexenyl, aminoalkyls), the latter generally donot represent more than 2% of the weight of the oil or of gum and notmore than 10% of the weight of the resin.

The viscous polydimethylsiloxane andα,ω-bis(hydroxy)polydimethylsiloxane oils and the polydimethylsiloxane,polyphenylmethylsiloxane and α,ω-bis(hydroxy)polydimethylsiloxane gumsare well known, commercial products.

The viscous polymethylsiloxane resins DT containing from 1 to 2% byweight of silanol functional groups are also commercial products.

The silicone substances may comprise at least one filler, in particularan inorganic filler. In this case, the compositions are calledcompounds. The silicone substance/filler ratios range in particular from2 to 15, preferably from 2 to 10.

The inorganic filler is preferably silica.

It may be precipitated silica or fumed silica, treated or not.

The precipitated silica is preferably prehydrophobized by conventionaltreatment with one or more organosilicon compounds. It may also beincorporated untreated, and then treated (hydrophobized) in situ withone or more organosilicon compounds. Among these compounds aremethylpolysiloxanes such as hexamethyldisiloxane,octamethylcyclotetrasiloxane, methylpolysilazanes such ashexamethyldisilazane, hexamethylcyclotrisilazane, chlorosilanes such asdimethyldichlorosilane, trimethylchlorosilane,methylvinyldichlorosilane, dimethylvinylchlorosilane, alkoxysilanes suchas dimethylmethoxysilane. During this treatment, the silicas canincrease their initial weight up to a level of 20%.

The fumed silica may be used untreated. If necessary, it can however betreated like the precipitated silica.

It is also possible to use in addition to or in place of the siliceousfillers other inorganic fillers such as ground quartz, calcined clay anddiatomaceous earth.

The inorganic fillers generally have a specific surface area, measuredaccording to the BET methods, of at least 50 m²/g, in particular ofbetween 50 and 400 m²/g, preferably of greater than 70 m²/g, a meanparticle size of less than 0.1 micrometer (μm) and an apparent densityof less than 200 g/liter.

In addition to the filler described above, the silicone substance maycomprise at least one surfactant, which is preferably nonionic.

By way of suitable nonionic surfactants, there may be mentioned forexample:

-   -   alkoxylated fatty alcohols, more particularly comprising from 6        to 22 carbon atoms;    -   alkoxylated mono-, di- and triglycerides;    -   alkoxylated fatty acids, more particularly comprising from 6 to        22 carbon atoms;    -   alkoxylated sorbitan esters, in particular cyclized sorbitol        esters of fatty acids comprising from 10 to 20 carbon atoms;    -   alkoxylated fatty amines, more particularly comprising from 6 to        22 carbon atoms;    -   alkoxylated alkylphenols, more particularly comprising one or        two linear or branched alkyl groups having 4 to 12 carbon atoms;    -   alkyl polyglucosides; alone or as mixtures.

If the surfactant is present, its content is advantageously from 5 to10% by weight relative to the weight of the silicone substance and,where appropriate, of the filler.

According to a second embodiment of the present invention, the substancehaving antifoam properties is chosen from perfluoroalkylphosphonicacids, perfluoroalkylphosphinic acids, perfluoroalkylphosphoric acids,or their alkali metals or ammonium salts.

More particularly, the alkyl radicals comprise 6 to 18 carbon atoms.

The salts may be salts of alkali metals, such as sodium or potassium,but also of ammonium of formula NR₄ ⁺; in which formula R, which areidentical or different, represent a hydrogen atom, an alkyl radicalcomprising 1 to 18 carbon atoms, optionally bearing at least onehydroxyl or amine group which is optionally ethoxylated.

These products are known to persons skilled in the art and are describedin particular in patent U.S. Pat. No. 5,332,714.

According to the invention, the solvent/substance weight ratio isbetween 99.95/0.05 and 90/10, preferably between 99.8/0.2 and 98/2.

Moreover, the aqueous formulation comprises 0.01 to 5% by weight ofmixture (solvent/substance), preferably 0.1 to 2% by weight of theaqueous formulation.

It should be noted that depending on the fields of application, theaqueous formulations may be used either as such, or after dilution.

The aqueous formulations comprising the mixture described above can havenumerous applications.

Thus, these formulations can be used in the field of the exploitation ofoil or gas deposits, as cementation fluid, as drilling fluid, or even asfracturing fluid.

Drilling fluids are conventionally fluids whose rheological propertiesare of the rheofluidizing type.

Generally, the fluids comprise polysaccharides such as galactomannans,such as guar; natural or chemically modified (partially or completelydeacetylated and/or depyruvylated) xanthan gum or alternatively xanthangum obtained after genetic modification of the strain producing it.

The polysaccharide content is usually between 0.01 and 2% by weightrelative to the total weight of the drilling fluid.

The drilling fluid further comprises salts which are soluble or at leastpartially soluble in the fluid, inorganic and optionally organic acids.

Among the salts of inorganic acids, there may be mentioned alkali oralkaline-earth metal halides, such as sodium, potassium or magnesiumchloride or bromide. It is likewise possible to use alkali oralkaline-earth metal sulfates, carbonates, bicarbonates, silicates orphosphates alone or as a mixture.

Among the salts of organic acids, there may be mentioned most especiallyalkali or alkaline-earth metal formates, or alkali or alkaline-earthmetal acetates.

It is likewise possible to use a salt chosen from silicates, preferablythose for which the Na₂O/SiO₂ molar ratio is close to 1/2, optionallycombined with the salts mentioned above.

The salt content is more particularly between 5000 and 110 000 ppm.

The drilling fluid may also comprise a filtrate control reducer orfiltrate reducer.

By way of examples of this type of compounds, there may be mentionedcellulosic compounds (in particular carboxymethylcelluloses,hydroxyethylcelluloses), polyacrylamides, polyacrylates of highmolecular weight, succinoglycans, native starch or its derivatives,charcoal.

The quantity of filtrate reducer greatly depends on the nature of therocks traversed while remaining nondetrimental because these compoundshave, for the most part, a Newtonian rheological profile. As a guide,the quantity of filtrate reducer is less than or equal to 1% relative tothe total weight of the fluid.

The drilling fluids may also comprise fluidizing or dispersing agents,such as polyphosphates, tannins, lignosulfonates, lignin derivatives,peats and lignites, polynaphthalene sulfonates, alone or as a mixture.

The quantity of fluidizing or dispersing agent is variable but generallyremains less than or equal to 1% relative to the total weight of thefluid.

The drilling fluid according to the invention may additionally comprisean oxygen scavenger so as to avoid any degradation of some additives.For example, hydroxylamines, hydrazine, sulfites, bisulfites,hydrosulfites, and borohydrides are suitable oxygen scavengers.

Generally, the content of additive of this type is less than or equal to0.25%.

The drilling fluid may furthermore comprise a weighting compound and/orat least one inorganic colloid.

The weighting components contribute toward maintaining a sufficienthydrostatic pressure in the well and toward maintaining in suspensionthe rocks carried during the drilling operation. Such compounds areconventionally chosen from the soluble salts mentioned above and thesparingly or very sparingly soluble salts, such as alkaline-earth metalsulfates, silicates or carbonates, of the barium sulfate or calciumcarbonate type. It is likewise possible to use alkaline-earth metal orzinc bromides such as potassium bromide or zinc bromide.

The inorganic colloids, which are compounds substantially insolubleunder the conditions for using the fluid, are agents modifying therheology of the medium and making it possible to maintain the debris insuspension in the latter. Attapulgite, barite, bentonite, alone or as amixture, are the most common examples thereof.

Other additives may be used, such as inorganic salts promoting theprecipitation of divalent ions, compounds limiting the swelling ofclays, free radical transfer agents, biocides, anticorrosion agents andthe like.

As regards the cementation fluids used for cementation of wells, thelatter comprise a hydraulic binder.

Compounds capable of reacting and hardening when they are in thepresence of water may be used; they are conventionally compounds basedon silicon, aluminum, calcium, oxygen and/or sulfur. For example,compounds based on calcium silicate (Portland cement), pozzolana,gypsum, hydraulic binders with high aluminum content, hydraulic bindersbased on phosphate and hydraulic binders based on calcium silicate, arepreferred.

It should be noted that the cementation fluid may comprise conventionaladditives in the field, such as for example filtrate reducing agents,caking retardants or accelerants, dispersant agents, rheology modifiers,thickening agents, air carrying agents, agents preventing the migrationof gases, and the like.

Usually, the total content of these additives, when they are present,does not exceed 30% by weight of hydraulic binder.

The cementation fluid may additionally comprise fillers. By way ofnonlimiting examples of inorganic fillers which may be used, there maybe mentioned calcium carbonate, fly ash, silica, fumed silica, clays(kaolin, metakaolin, bentonite, sepiolite, wollastonite), mica,feldspar, silicate, glass, titanium dioxide, aluminum or magnesia.

Expanded polystyrene may be used in particular as organic filler.

The mean size of inorganic fillers is advantageously less than or equalto 120 μm, preferably less than or equal to 80 μm.

The content of fillers in the cement, when they are present, variesaccording to the subsequent applications for which the cement isintended. Likewise, depending on whether it is desired to make thelatter denser or lighter, inorganic or organic fillers may be used.

Here again, without intending to be limiting thereto, the content offillers represents at most the same weight as the hydraulic binder.

It should be noted that the cementation fluid may comprise long or shortreinforcing fibers. These fibers may be either metallic or polymeric.Advantageously, the polymeric fibers are polyamide, polyvinyl alcohol,polyethylene or polypropylene fibers, and the like. The size of thereinforcing fibers may vary within a broad range. By way of example, thesize can vary between a few tenths of millimeter to several tens ofmillimeter.

As for the content of fluid in these fibers, it can be easily evaluatedby a person skilled in the art. It is usually less than or equal to 10%relative to the hydraulic binder.

The cement, mortar and concrete compositions, and the like, intended forthe building materials industry may likewise comprise the mixtureaccording to the invention.

Such compositions are of the same type as those which have just beendescribed above in the context of the cementing of wells.

They may also comprise granular components which are usually chosen fromsand, silicon dioxide, titanium, alumina, talc, mica, (meta)kaolin,bentonite, clinker, vermiculite, perlite, cellulose, slag. They may becrystallized or amorphous synthetic products obtained for example bygrinding, and sieving to the desired size.

It is also possible to use ground silica, pyrogenic silica and fly ash.

The particle size distribution of the granular components can varywidely depending on the application envisaged. The size of the granularcomponents can vary for example between 1 and 500 μm.

According to another possibility, the aqueous formulations comprisingthe mixture can be used in the paper industry.

They can be used in particular as paper coating bath.

The formulations comprise pigment-type fillers. They may be inorganicpigments such as kaolin, white satin, talc, calcium carbonate, titaniumoxide, inter alia, or alternatively plastic pigments.

The formulation further comprises binders, whether they are of thenatural type, such as starches, or of the synthetic type, such aslatexes.

Generally, the latexes are obtained from unsaturated monomers such asvinyl, acrylic or vinylaromatic monomers, vinyl esters, alkyl esters ofunsaturated acids, esters of unsaturated carboxylic acids, vinylchloride, vinylidene chloride and/or dienes. Among the suitable latexes,there may be mentioned styrene/butadiene, styrene/acrylate andstyrene/butadiene/acrylate latexes, and the like.

Usually, the binders are present in an amount of 5 to 25 parts by weightper 100 parts by weight of pigment.

The formulations may likewise comprise an optical brightener, in anamount of 0.1 to 0.7 parts by weight, preferably combined with anoptical brightener carrier such as polyvinyl alcohol with a contentusually of between 0.2 and 2 parts by weight.

The formulations preferably comprise a thickening agent. Such compoundsmake it possible to control the rheology of the formulation. This mayinclude alkali-soluble copolymers comprising a combination of severalmonomers such as carboxylated ethylenically unsaturated compounds,nonionic vinyl monomers and monomers and ethylenically unsaturatednonionic amphiphilic monomers.

The formulations may also comprise slip agents such as calcium stearate,and insolubilizing agents.

Usually, dry matter content of the formulation is 60 to 75% by weight.

According to certain applications, the compositions for a coating bathmay also comprise resins such as epoxy resins, provided in the form ofan emulsion.

These resins may be chosen in particular from aromatic epoxy resins ofthe Novolak type, epoxy resins of the bisphenol-A type.

The emulsions additionally comprise a nonionic surfactant, such aspolyethylene and/or polypropylene oxides, alkylaromatic ethers ofpolyethylene and/or polypropylene glycol, polyoxyalkylene derivatives ofhexitol including sorbitans and mannitans.

The mixture according to the invention may likewise be used informulations intended for making laminated compounds, in whichformulations melamine-formalin or urea-formalin resins are present; andin formulations for adhesive compositions.

The aqueous formulations comprising the solvent/substance mixture caneven be used in the field of deformation or transformation of metals,such as in particular operations of wiredrawing and rolling, fordeformation, and cutting work, for transformation.

The aqueous formulations conventionally used are provided inconcentrated form which the user dilutes before carrying out the workingof the metal.

The solvent/substance mixture may be used in aqueous formulations ofthis type.

Among the products capable of entering into the composition of suchformulations are saturated or unsaturated carboxylic acids comprising atleast 5 carbon atoms. More particularly, these acids are chosen fromsaturated or unsaturated mono- or polycarboxylic acids comprising 5 to40 carbon atoms. By way of example, there may be mentioned palmitic,behenic, stearic, palmitoleic, oleic, petroselenic, erucic, linoleic,linolenic and ricinoleic acids, alone or as mixtures.

Said acid may optionally be in a form neutralized with an inorganic base(alkali metal hydroxides, hydroxycarbonates and (bi)carbonates, and thelike, aqueous ammonia) or an organic base (primary, secondary ortertiary amines optionally substituted with one or more OH radicals, oran alkoxylated radical).

The formulations may even comprise acid phosphate esters having at leastone saturated or unsaturated aliphatic, cycloaliphatic or aromatichydrocarbon radical containing 1 to 30 carbon atoms, which is optionallypolyalkoxylated (polyoxyethylenated and/or polyoxypropylenated).

The formulations may comprise, where appropriate, a nonionic surfactantin an amount of 5% maximum relative to the total weight of theformulation after dilution, such as polyalkoxylated alkylphenols,polyalkoxylated C₈-C₂₂ aliphatic alcohols, polyalkoxylatedtriglycerides, and the like).

The aqueous formulations may furthermore be used in the field ofcleaning and/or degreasing surfaces. The expression cleaning surfaces isunderstood to mean the cleaning of textiles (laundry) and the cleaningof hard surfaces, in particular dishes, domestic surfaces, andindustrial surfaces. The formulations for cleaning textile surfaces maybe laundry detergents for washing by hand or in a machine. Theformulations for washing dishes may be products for washing dishes byhand or in a machine. In these formulations, it is often desirable tocontrol foaming. Moreover, there is great interest in homogeneous, oreven transparent, formulations.

The aqueous formulations for degreasing sheet metals are preferablyalkaline formulations.

As a guide, the content of mixture during the use of these formulations,which are often in dilute form, is of the order of 0.01 to 5 g/l.

They additionally comprise:

-   -   of the order of 0 to 2%, generally 0.01 to 1% by weight (in the        aqueous formulation) of at least one anionic or nonionic        detergent surfactant such as (C₈-C₁₆)alkylbenzenesulfonates,        (C₈-C₂₀)alkyl sulfates, ethoxylated alkylphenols, ethoxylated        fatty alcohols, block polymers of ethylene oxide and propylene        oxide,    -   of the order of 5 to 20% by weight (in an aqueous formulation)        of at least one hydrotropic electrolyte such as        benzenesulfonates, mono- or di(C₁-C₄)alkylbenzenesulfonates,        toluene-, xylene- or cumene-sulfonates,    -   other hydrotropic agents, such as alcohols and glycols,    -   of the order of 5 to 25% by weight (in the aqueous formulation)        of at least one sequestering agent such as nitriloacetic acid,        ethylenediaminetetraacetic acid,        ethylenediaminetetramethylphosphonic acid,        nitrilotrimethylenephosphonic acid and their salts,    -   buffering agents such as alkanolamines, ethylenediamine and the        like.

In the field of petroleum oil exploitation, and more particularly of thedegreasing of platforms, the aqueous formulations comprise of the orderof 0.005 to 0.05 g/l, preferably of the order of 0.015 to 0.025 g/l ofthe formulation (after dilution) as a mixture.

The aqueous compositions used for degreasing oil platforms may comprise,in addition to the solvent/substance mixture:

-   -   of the order of 0 to 2%, generally 0.01 to 1% by weight (in the        aqueous formulation) of at least one anionic or nonionic        detergent surfactant such as (C₈-C₁₆)alkylbenzenesulfonates,        (C₈-C₂₀)alkyl sulfates, ethoxylated alkylphenols, ethoxylated        fatty alcohols, block polymers of ethylene oxide and propylene        oxide,    -   of the order of 5 to 20% by weight (in the aqueous formulation)        of at least one hydrotropic electrolyte such as        benzenesulfonate, mono- or di(C₁-C₄)alkylbenzenesulfonates,        toluene-, xylene- or cumene-sulfonates,    -   other hydrotropic agents, such as alcohols and glycols,    -   at least one pH-regulating agent such as for example alkali        metal carbonates, sesquicarbonates and bicarbonates,    -   additives such as enzymes in a quantity which may be up to 5% of        the total weight of the aqueous fluid, and metal corrosion        inhibitors.

The aqueous formulations used for cleaning oil wells comprise, inaddition to the mixture:

-   -   3 to 40% by weight of the aqueous medium of anionic surfactants        (alkyl ester sulfonates, alkyl sulfates, salts of C₈-C₂₄ fatty        acids, saturated or unsaturated, C₉-C₂₀ alkylbenzenesulfonates,        alkyl sulfonates, and the like), nonionic surfactants        (polyoxyalkylenated alkylphenols, polyoxyalkylenated C₈-C₂₂        aliphatic alcohols, products resulting from the condensation of        ethylene oxide, the compound resulting from the condensation of        propylene oxide with propylene glycol, and the like);    -   an agent allowing the pH to be adjusted, such as for example        alkali metal carbonates, sesquicarbonates and bicarbonates,        alkali or alkaline-earth metal hydroxides,    -   additives such as enzymes in a quantity which may be up to 5% of        the total weight of the aqueous fluid, and metal corrosion        inhibitors,    -   if necessary, weighting agents so as to maintain a sufficient        hydrostatic pressure in the well. Reference may be made to the        list given in the context of the description of the constituent        elements of drilling fluids;    -   hydrocolloids such as polysaccharides of plant origin, such as        polygalactomannans and their derivatives, such as guar,        hydroxypropylguar; cellulose and its derivatives, starches and        their derivatives; polysaccharides of bacterial origin such as        xanthan gum or deacetylated derivatives.

The aqueous formulations may also be used in the field of water paints,or coatings.

Paints, in addition to the mixture according to the invention, comprisein general a binder and at least one additional component chosen fromfillers, pigments, surfactants, thickeners, antioxidants, naturalbinders, dispersing agents, biocides, and the like.

Usually, the binders are latexes prepared from unsaturated ethylenicmonomers.

Among the appropriate monomers, there may be mentioned most especiallystyrene, butadiene, acrylic esters and vinyl nitrites.

It is likewise possible to include, during the preparation of saidlatexes, unsaturated ethylenic monomers having a crosslinkable charactersuch as glycidyl (meth)acrylate or vinyl and acrylic silanes. If theyare present, their content generally does not exceed 0.1 to 5% of theunsaturated ethylenic monomers mentioned above.

The particle size of the latexes is more particularly between 100 and500 nm.

Furthermore, it is possible to combine the latex with a nanolatex whosesize is between 5 and 40 nm.

These nanolatexes may be homopolymers or copolymers containing unitsderived from vinyl, acrylic or vinylaromatic monomers, vinyl esters,alkyl esters of unsaturated acids, esters of unsaturated carboxylicacids, vinyl chloride, vinylidene chloride and/or dienes.

Moreover, the latex binder is preferably neutralized with a base (forexample aqueous ammonia or an amine).

The composition further comprises pigments such as zinc or titaniumdioxide, zinc sulfides, iron oxides, molybdates or chromates, and thelike.

It may even comprise calcium carbonates, talc, baryta, silica, mica,diatomaceous earths, and the like.

The content of these compounds is determined in a conventional manner inthe field, so as to obtain good covering properties and good mechanicalproperties. As a guide, their content varies between 10 and 50% byvolume.

In accordance with another embodiment of the invention, the aqueousformulations may be intended for the treatment of plants.

Advantageously, the formulations are in the form of concentratedsolutions.

They comprise, moreover, at least one plant-protection active material,which is soluble and stable (that is to say which is not substantiallyhydrolyzed) in aqueous medium, at the chosen concentration.

By way of example, the concentration of active material(s) in theformulation is less than or equal to 540 g/l expressed relative to theactive material, more particularly between 100 and 540 g/l, preferablybetween 100 and 500 g/l. It should be noted that when the activematerial is present in salified form, the ranges which have just beenindicated are expressed relative to the active material in nonsalifiedform.

According to a preferred embodiment of the invention, theplant-protection active materials are chosen from hydrophilicpesticides, and more especially herbicides, but also hydrophilicnutritive elements promoting the growth and development of plants.

Preferably, said active materials are in the form of organic orinorganic salts.

Among the suitable active materials, there may be mentioned inparticular the following herbicidal active materials in the form oforganic or inorganic salts: aminophosphate or aminophosphonatederivatives, Acifluorfen, Asulam, Bentazon, Bialaphos, Bispyribac,Bromacil, Bromoxynil, Chloramben, Clopyralid, 2,4-D, 2,4-Db, Dalapon,Dicamba, Dichloprop, Difenzoquat, Diquat, Endothall, Fenac, Fomesafen,Fosamine, Ioxynil, MCPA, MCPB, Mecoprop, Methylarsonic Acid, Naptalam,Paraquat, Picloram, Sulfamic Acid, alone or as a mixture.

Preferably, the active material is chosen from aminophosphate oraminophosphonate derivatives, in the form of organic or inorganic salts,such as glyphosate, sulphosate, glufosinate, in the form of organic orinorganic salts.

The expression glyphosate denotes more particularlyN-phosphonomethylglycine and any derivative thereof leading in aqueoussolution to glyphosate anions.

As suitable salts, there may be mentioned more particularly the salts ofalkali metals such as sodium or potassium; ammonium salts, of the N(R)₄⁺ type for which the radicals R, which are identical or different,represent a hydrogen atom or saturated or unsaturated, linear ornonlinear C₁-C₆ hydrocarbon radical optionally substituted with ahydroxyl group; or alternatively sulfonium salts; said salts beingpresent alone or in combination.

Among the ammonium salts, there may be mentioned most particularlysecondary or primary amines such as isopropylamine, dimethylamine ordiamines such as ethylenediamine; amines bearing a hydroxyl group suchas monoethanolamine. As for the sulfonium salts, trimethylsulfonium isperfectly suitable.

As preferred glyphosate derivatives, there may be mentioned inparticular the isopropylamine salt and the trimethylsulfonium salt.

As regards the nutritive elements, they are preferably metal salts suchas zinc, iron and preferably manganese salts. These salts are used inthe form of chelates of the EDTA type for example or of sulfates.

According to one variant of the invention, the plant-protectionformulation comprises at least one biological activator of theplant-protection active material.

By way of examples of biological activators, there may be mentioned inparticular polyalkoxylated amines (more especially comprising at leastone hydrocarbon radical having from 4 to 30 carbon atoms) and inparticular polyethoxylated amines; polyalkoxylated (for examplepolyethoxylated or polyethoxylated/polypropoxylated) amidoamines. Alsosuitable are the polyalkoxylated (for example polyethoxylated orpolyethoxylated/polypropoxylated) mono- and diphosphate esters ofsaturated or unsaturated, linear or nonlinear aliphatic hydrocarbonalcohols comprising more particularly 4 to 30 carbon atoms, or ofaromatic alcohols (more particularly those for which the aromatic ringcomprises 6 carbon atoms) optionally comprising one or more substituentson the aromatic ring, chosen from alkyl radicals, alkenyl radicals,comprising up to 30 carbon atoms, or chosen from alkylaryl radicals forwhich the linear or nonlinear alkyl part comprises 1 to 10 carbon atomsand the aryl part comprises 6 carbon atoms; the counterion is generallychosen from alkali metals such as sodium or potassium, ammonium ions ofthe NR₄ ⁺ type with R, which are identical or different, representing ahydrogen atom, an alkyl radical comprising 1 to 10 carbon atoms,preferably 1 to 4, optionally bearing a hydroxyl radical.

Among the biological activators which can be envisaged, there may alsobe mentioned inorganic salts which are soluble in the aqueous phase,such as for example the salts of alkali metals, such as sodium orpotassium, or of ammonium of the compounds chosen from carbonates;bicarbonates; halides, such as chlorides, fluorides; nitrates,phosphates; hydrogen phosphates; sulfates; bisulfates; bisulfides, aloneor as a mixture.

The activators which have just been mentioned may be used alone or asmixtures.

It should be noted furthermore that the quantity of biological activatorgenerally represents 10 to 70% by weight relative to theplant-protection active material(s), preferably between 20 and 60% byweight.

Finally, a final subject of the invention consists of an aqueousformulation comprising from 0.01 to 5% by weight of a mixture comprisingat least one solvent and at least one substance having antifoamproperties in aqueous medium; the solvent/substance weight ratio beingbetween 99.95/0.05 and 90/10; said solvent being chosen from those forwhich, in all or part of the range of weight ratio mentioned above, themixture is homogeneous and from those for which the aqueous formulation,comprising from 0.01 to 5% by weight of mixture, is homogeneous.

What was detailed above in relation to the nature of the variousconstituent elements of the mixture and their contents remains valid andwill not be described again.

In addition, the formulations comprise the customary additives,depending on the fields in which they are used. Here again, referencemay be made to the appropriate passages of the description.

The formulations are quite obviously obtained by mixing the componentsconstituting them.

A concrete but nonlimiting example of the invention will now bepresented.

EXAMPLE

A plant-protection formulation is prepared which comprises glyphosate inthe form of an isopropylamine salt, and whose glyphosate concentrationis 360 g/l expressed as acid equivalent, by mixing the followingcompounds, with stirring: Isopropylamine salt of 360 g/l expressed asglyphosate glyphosate in acid form Tallow amine comprising 170 g/l 15 EOWater qs 1 liter

In the control trial, the foam test is performed on the formulationdescribed above, without adding antifoaming/defoaming agent.

The trial according to the invention is a formulation as described abovecomprising 1% of a 99/1 mixture by weight respectively of Phytorob®810.01 (comprising a mixture of C₈-C₁₀ methyl esters and marketed by thecompany Novance) and Rhodorsil® 481 (marketed by the company RhodiaChimie). The formulation obtained is clear and stable during storage.Such a mixture is marketed in particular by the company Rhodia under thename Geronol CF/AR.

The foam test (CIPAC MT 47, foam persistence, Cipac Handbook F page 152)is as follows:

-   -   0.5 ml of the composition to be tested is added to a graduated        cylinder with 50 ml of water (Cipac D water).

The cylinder is stoppered and 30 complete inversions are made, allowingon each inversion the air bubble to rise to the top part.

The cylinder is unstoppered and the foam volume is measured at 10seconds, 1 minute, 3 minutes and 12 minutes.

The table below gives the foam volume in ml for each of the trials, atthe times mentioned: Time 1 second 1 minute 3 minutes 12 minutes Control50 39 16 5 Invention 29 8 5 3

A formulation comprising 1% of Rhodorsil® 481, without solvent, iscloudy and is not stable during storage.

A formulation comprising 1% of Phytorob® 810.01, without Rhodorsil® 481,is clear and stable during storage. On the other hand, the level ofdefoaming is much less high than that obtained with the mixtureaccording to the invention.

1-21. (canceled)
 22. A process for providing antifoam properties to anaqueous formulation, comprising the step of adding to said formulationan efficient amount of a mixture comprising at least one solvent and atleast one substance having antifoam properties in aqueous medium; with asolvent/substance weight ratio being between 99.95/0.05 and 90/10; saidsolvent being chosen from those for which, in all or part of the rangeof the abovementioned weight ratio, the mixture is homogeneous, and fromthose for which the aqueous formulation, comprising from 0.01 to 5% byweight of mixture, is homogeneous.
 23. The process as claimed in claim22, wherein the solvent is: an ester of saturated or unsaturated, linearor branched mono or dicarboxylic acids comprising 2 to 15 carbon atoms,optionally comprising an alkoxy group, preferably a methoxy group, or ahydroxyl group, and of a saturated or unsaturated, linear or branchedmonoalcohol or polyol comprising 1 to 13 carbon atoms; a mono-, di-and/or triester phosphate for which the radical(s), which are identicalor different, are linear or branched alkyl radicals bearing 2 to 12carbon atoms; a ketone for which the radicals, which are identical ordifferent, are linear or branched alkyl radicals comprising 1 to 5carbon atoms; a heterocyclic derivative comprising at least one nitrogenand/or at least one oxygen and/or at least one sulfur; or a mono- orpolyethers of polyalcohols.
 24. The process as claimed in claim 22,wherein the substance having antifoam properties is a siliconecomprising units of formulae:R′_(3-a)R_(a)SiO_(1/2) and R₂SiO_(2/2) wherein: a is an integer from 0to 3 the radicals R are identical or different and represent a saturatedor unsaturated aliphatic hydrocarbon group containing from 1 to 10carbon atoms; a polar organic group attached to the silicon by a Si—C orSi—O—C bond; or an aromatic hydrocarbon group containing from 6 to 13carbon atoms; the radicals R′ are identical or different and representan OH group; an alkoxy or alkenyloxy group containing from 1 to 10carbon atoms; an aryloxy group containing from 6 to 13 carbon atoms; anacyloxy group containing from 1 to 13 carbon atoms; a cetiminoxy groupcontaining from 1 to 8 carbon atoms; or an amino or amido functionalgroup containing from 1 to 6 carbon atoms, attached to the silicon by anSi—N bond; optionally, at least 80% of the radicals R representing amethyl group.
 25. The process as claimed in the preceding claim 22,wherein the silicone substance comprises at least one filler.
 26. Theprocess as claimed in claim 25, wherein the silicone substance presentsa silicone substance/filler weight ratio from 2 to 15, optionally from 2to
 10. 27. The process as claimed in claim 22, wherein the siliconesubstance further comprises at least one surfactant, which is optionallynonionic.
 28. The process as claimed in claim 27, wherein the surfactanthas a content from 5 to 10% by weight relative to the weight of thesilicone substance and, optionally, of filler.
 29. The process asclaimed in claim 22, wherein the substance having antifoam properties isa perfluoroalkylphosphonic acid, perfluoroalkylphosphinic acid,perfluoroalkylphosphoric acids or their alkali metal or ammonium salts.30. The process as claimed in claim 22, wherein the solvent presents asolvent/substance weight ratio of between 99.8/0.2 and 98/2.
 31. Theprocess as claimed in claim 22, wherein 0.01 to 5% by weight of themixture is added to the aqueous formulation, optionallly 0.1 to 2%. 32.The process as claimed in claim 22, wherein the aqueous formulations isto be used in the field of the exploitation of oil or gas deposits. 33.The process as claimed in claim 22, wherein the aqueous formulation isto be used in the paper industry.
 34. The process as claimed in claim22, wherein the aqueous formulation is to be used in the field of thedeformation or the transformation of metals.
 35. The process as claimedin claim 22, wherein the aqueous formulation is to be used in the fieldof the cleaning and/or the stripping of surfaces.
 36. The process asclaimed in claim 22, wherein the aqueous formulation is to be used inthe field of water paints, coatings, laminates or adhesives.
 37. Theprocess as claimed in claim 22, wherein the aqueous formulation is to beused in the field of building materials.
 38. The process as claimed inclaim 22, wherein the aqueous formulation is to be used for thetreatment of plants.
 39. The process as claimed in the claim 38, whereinthe aqueous formulation comprises at least one plant-protection activematerial which is an aminophosphate or an aminophosphonate, in the formof organic or inorganic salts.
 40. The process as claimed in the claim39, wherein the plant-protection active material is a glyphosate,sulfosate, or a glufosinate, in the form of organic or inorganic salt.41. The process as claimed in claim 40, wherein the plant-protectionactive material is present in the formulation in a concentration of lessthan or equal to 540 g/l, expressed relative to the nonsalified activematerial.
 42. The process as claimed in claim 41, wherein saidconcentration is between 100 and 540 g/l.
 43. The process as claimed inclaim 40, wherein the formulation further comprises at least onebiological activator of the plant-protection active material.
 44. Anaqueous formulation comprising from 0.01 to 5% by weight of a mixturecomprising at least one solvent and at least one substance havingantifoam properties in aqueous medium; with a solvent/substance weightratio being between 99.95/0.05 and 90/10; said solvent being chosen fromthose for which, in all or part of the range of the abovementionedweight ratio, the mixture is homogeneous, and from those for which theaqueous formulation, comprising from 0.01 to 5% by weight of mixture, ishomogeneous.